JP4652170B2 - Polypropylene production method - Google Patents
Polypropylene production method Download PDFInfo
- Publication number
- JP4652170B2 JP4652170B2 JP2005234500A JP2005234500A JP4652170B2 JP 4652170 B2 JP4652170 B2 JP 4652170B2 JP 2005234500 A JP2005234500 A JP 2005234500A JP 2005234500 A JP2005234500 A JP 2005234500A JP 4652170 B2 JP4652170 B2 JP 4652170B2
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- Prior art keywords
- compound
- carbon atoms
- polymerization
- general formula
- magnesium
- Prior art date
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- -1 Polypropylene Polymers 0.000 title claims description 85
- 239000004743 Polypropylene Substances 0.000 title claims description 27
- 229920001155 polypropylene Polymers 0.000 title claims description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 60
- 238000006116 polymerization reaction Methods 0.000 claims description 56
- 125000004432 carbon atom Chemical group C* 0.000 claims description 37
- 239000002904 solvent Substances 0.000 claims description 30
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 29
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 28
- 230000009849 deactivation Effects 0.000 claims description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 239000002685 polymerization catalyst Substances 0.000 claims description 9
- 125000002252 acyl group Chemical group 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 238000010791 quenching Methods 0.000 claims description 6
- 230000000171 quenching effect Effects 0.000 claims description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 239000003054 catalyst Substances 0.000 description 69
- 239000010936 titanium Substances 0.000 description 68
- 229910052719 titanium Inorganic materials 0.000 description 49
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 47
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 36
- 239000007787 solid Substances 0.000 description 32
- 150000002681 magnesium compounds Chemical class 0.000 description 23
- 239000000178 monomer Substances 0.000 description 16
- 150000002430 hydrocarbons Chemical group 0.000 description 15
- 239000004927 clay Substances 0.000 description 12
- 229910052736 halogen Inorganic materials 0.000 description 12
- 150000002367 halogens Chemical class 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 239000002734 clay mineral Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 10
- 239000000460 chlorine Substances 0.000 description 10
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 10
- 239000002002 slurry Substances 0.000 description 10
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 9
- 229910004298 SiO 2 Inorganic materials 0.000 description 9
- 229910052723 transition metal Inorganic materials 0.000 description 9
- 150000003624 transition metals Chemical class 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 150000003961 organosilicon compounds Chemical class 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 150000003609 titanium compounds Chemical class 0.000 description 5
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 4
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000005234 alkyl aluminium group Chemical group 0.000 description 3
- 150000005215 alkyl ethers Chemical class 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 3
- 150000001733 carboxylic acid esters Chemical class 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- JQCXWCOOWVGKMT-UHFFFAOYSA-N diheptyl phthalate Chemical compound CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 description 3
- MQHNKCZKNAJROC-UHFFFAOYSA-N dipropyl phthalate Chemical compound CCCOC(=O)C1=CC=CC=C1C(=O)OCCC MQHNKCZKNAJROC-UHFFFAOYSA-N 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002484 inorganic compounds Chemical class 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 150000002902 organometallic compounds Chemical class 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- HBEDSQVIWPRPAY-UHFFFAOYSA-N 2,3-dihydrobenzofuran Chemical compound C1=CC=C2OCCC2=C1 HBEDSQVIWPRPAY-UHFFFAOYSA-N 0.000 description 2
- HPYNZHMRTTWQTB-UHFFFAOYSA-N 2,3-dimethylpyridine Chemical compound CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 2
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 description 2
- WNZQDUSMALZDQF-UHFFFAOYSA-N 2-benzofuran-1(3H)-one Chemical compound C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Natural products CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 208000005156 Dehydration Diseases 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- WEEGYLXZBRQIMU-UHFFFAOYSA-N Eucalyptol Chemical compound C1CC2CCC1(C)OC2(C)C WEEGYLXZBRQIMU-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- 239000004166 Lanolin Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- HOPRXXXSABQWAV-UHFFFAOYSA-N anhydrous collidine Natural products CC1=CC=NC(C)=C1C HOPRXXXSABQWAV-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- SESFRYSPDFLNCH-UHFFFAOYSA-N benzyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC1=CC=CC=C1 SESFRYSPDFLNCH-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical group O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
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- RPNFNBGRHCUORR-UHFFFAOYSA-N diethyl 2-butylpropanedioate Chemical compound CCCCC(C(=O)OCC)C(=O)OCC RPNFNBGRHCUORR-UHFFFAOYSA-N 0.000 description 1
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- DEMPTVYXFMKCIA-UHFFFAOYSA-N diethyl naphthalene-1,2-dicarboxylate Chemical compound C1=CC=CC2=C(C(=O)OCC)C(C(=O)OCC)=CC=C21 DEMPTVYXFMKCIA-UHFFFAOYSA-N 0.000 description 1
- FGYDHYCFHBSNPE-UHFFFAOYSA-N diethyl phenylmalonate Chemical compound CCOC(=O)C(C(=O)OCC)C1=CC=CC=C1 FGYDHYCFHBSNPE-UHFFFAOYSA-N 0.000 description 1
- JJSGABFIILQOEY-UHFFFAOYSA-M diethylalumanylium;bromide Chemical compound CC[Al](Br)CC JJSGABFIILQOEY-UHFFFAOYSA-M 0.000 description 1
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- OSZVQUZIQCJAPJ-UHFFFAOYSA-N dimethoxy-bis(2-methylcyclopentyl)silane Chemical compound C1CCC(C)C1[Si](OC)(OC)C1CCCC1C OSZVQUZIQCJAPJ-UHFFFAOYSA-N 0.000 description 1
- VWSCOSAMLOTWPA-UHFFFAOYSA-N dimethoxy-bis(3-methylcyclopentyl)silane Chemical compound C1CC(C)CC1[Si](OC)(OC)C1CCC(C)C1 VWSCOSAMLOTWPA-UHFFFAOYSA-N 0.000 description 1
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical class CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- KZLUHGRPVSRSHI-UHFFFAOYSA-N dimethylmagnesium Chemical compound C[Mg]C KZLUHGRPVSRSHI-UHFFFAOYSA-N 0.000 description 1
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- TVWTZAGVNBPXHU-FOCLMDBBSA-N dioctyl (e)-but-2-enedioate Chemical compound CCCCCCCCOC(=O)\C=C\C(=O)OCCCCCCCC TVWTZAGVNBPXHU-FOCLMDBBSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- DWNAQMUDCDVSLT-UHFFFAOYSA-N diphenyl phthalate Chemical compound C=1C=CC=C(C(=O)OC=2C=CC=CC=2)C=1C(=O)OC1=CC=CC=C1 DWNAQMUDCDVSLT-UHFFFAOYSA-N 0.000 description 1
- OANIYCQMEVXZCJ-UHFFFAOYSA-N ditert-butyl(dimethoxy)silane Chemical compound CO[Si](OC)(C(C)(C)C)C(C)(C)C OANIYCQMEVXZCJ-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- PTOQCUYVGKZAFS-UHFFFAOYSA-N ethenylcycloheptane Chemical compound C=CC1CCCCCC1 PTOQCUYVGKZAFS-UHFFFAOYSA-N 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- IWYBVQLPTCMVFO-UHFFFAOYSA-N ethyl 2,2-dichloroacetate Chemical compound CCOC(=O)C(Cl)Cl IWYBVQLPTCMVFO-UHFFFAOYSA-N 0.000 description 1
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- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical group CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 1
- MGDOJPNDRJNJBK-UHFFFAOYSA-N ethylaluminum Chemical compound [Al].C[CH2] MGDOJPNDRJNJBK-UHFFFAOYSA-N 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- JVZRCNQLWOELDU-UHFFFAOYSA-N gamma-Phenylpyridine Natural products C1=CC=CC=C1C1=CC=NC=C1 JVZRCNQLWOELDU-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WZHKDGJSXCTSCK-UHFFFAOYSA-N hept-3-ene Chemical compound CCCC=CCC WZHKDGJSXCTSCK-UHFFFAOYSA-N 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002537 isoquinolines Chemical class 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 1
- 229910001641 magnesium iodide Inorganic materials 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- BSGVJBRWDNPHOR-UHFFFAOYSA-M magnesium;butan-1-olate;chloride Chemical compound [Mg+2].[Cl-].CCCC[O-] BSGVJBRWDNPHOR-UHFFFAOYSA-M 0.000 description 1
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 description 1
- QUXHCILOWRXCEO-UHFFFAOYSA-M magnesium;butane;chloride Chemical compound [Mg+2].[Cl-].CCC[CH2-] QUXHCILOWRXCEO-UHFFFAOYSA-M 0.000 description 1
- YJCTUQFSSZSZPO-UHFFFAOYSA-L magnesium;chloride;phenoxide Chemical compound [Cl-].[Mg+]OC1=CC=CC=C1 YJCTUQFSSZSZPO-UHFFFAOYSA-L 0.000 description 1
- BJZBHTNKDCBDNQ-UHFFFAOYSA-L magnesium;dodecanoate Chemical compound [Mg+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O BJZBHTNKDCBDNQ-UHFFFAOYSA-L 0.000 description 1
- DLPASUVGCQPFFO-UHFFFAOYSA-N magnesium;ethane Chemical compound [Mg+2].[CH2-]C.[CH2-]C DLPASUVGCQPFFO-UHFFFAOYSA-N 0.000 description 1
- YCCXQARVHOPWFJ-UHFFFAOYSA-M magnesium;ethane;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C YCCXQARVHOPWFJ-UHFFFAOYSA-M 0.000 description 1
- KRTCPMDBLDWJQY-UHFFFAOYSA-M magnesium;ethanolate;chloride Chemical compound [Mg+2].[Cl-].CC[O-] KRTCPMDBLDWJQY-UHFFFAOYSA-M 0.000 description 1
- RVOYYLUVELMWJF-UHFFFAOYSA-N magnesium;hexane Chemical compound [Mg+2].CCCCC[CH2-].CCCCC[CH2-] RVOYYLUVELMWJF-UHFFFAOYSA-N 0.000 description 1
- GBRJQTLHXWRDOV-UHFFFAOYSA-M magnesium;hexane;chloride Chemical compound [Mg+2].[Cl-].CCCCC[CH2-] GBRJQTLHXWRDOV-UHFFFAOYSA-M 0.000 description 1
- ZHLDMBMNKCIBQN-UHFFFAOYSA-M magnesium;methanolate;chloride Chemical compound [Cl-].CO[Mg+] ZHLDMBMNKCIBQN-UHFFFAOYSA-M 0.000 description 1
- CFXDAHURBQNVFG-UHFFFAOYSA-M magnesium;propan-2-olate;chloride Chemical compound [Mg+2].[Cl-].CC(C)[O-] CFXDAHURBQNVFG-UHFFFAOYSA-M 0.000 description 1
- RYEXTBOQKFUPOE-UHFFFAOYSA-M magnesium;propane;chloride Chemical compound [Mg+2].[Cl-].CC[CH2-] RYEXTBOQKFUPOE-UHFFFAOYSA-M 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- QABLOFMHHSOFRJ-UHFFFAOYSA-N methyl 2-chloroacetate Chemical compound COC(=O)CCl QABLOFMHHSOFRJ-UHFFFAOYSA-N 0.000 description 1
- WVWZECQNFWFVFW-UHFFFAOYSA-N methyl 2-methylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C WVWZECQNFWFVFW-UHFFFAOYSA-N 0.000 description 1
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- DDIZAANNODHTRB-UHFFFAOYSA-N methyl p-anisate Chemical compound COC(=O)C1=CC=C(OC)C=C1 DDIZAANNODHTRB-UHFFFAOYSA-N 0.000 description 1
- OLXYLDUSSBULGU-UHFFFAOYSA-N methyl pyridine-4-carboxylate Chemical compound COC(=O)C1=CC=NC=C1 OLXYLDUSSBULGU-UHFFFAOYSA-N 0.000 description 1
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- 125000005561 phenanthryl group Chemical group 0.000 description 1
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- 239000011574 phosphorus Substances 0.000 description 1
- SFLGSKRGOWRGBR-UHFFFAOYSA-N phthalane Chemical compound C1=CC=C2COCC2=C1 SFLGSKRGOWRGBR-UHFFFAOYSA-N 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
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- 235000010989 polyoxyethylene sorbitan monostearate Nutrition 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
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- 229940090181 propyl acetate Drugs 0.000 description 1
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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- 150000003233 pyrroles Chemical class 0.000 description 1
- ZVJHJDDKYZXRJI-UHFFFAOYSA-N pyrroline Natural products C1CC=NC1 ZVJHJDDKYZXRJI-UHFFFAOYSA-N 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
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- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 229960005078 sorbitan sesquioleate Drugs 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- ASEHKQZNVUOPRW-UHFFFAOYSA-N tert-butyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C(C)(C)C ASEHKQZNVUOPRW-UHFFFAOYSA-N 0.000 description 1
- JHVNMGWNEQGGDU-UHFFFAOYSA-N tert-butyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C(C)(C)C)OCC JHVNMGWNEQGGDU-UHFFFAOYSA-N 0.000 description 1
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- ZFDIRQKJPRINOQ-UHFFFAOYSA-N transbutenic acid ethyl ester Natural products CCOC(=O)C=CC ZFDIRQKJPRINOQ-UHFFFAOYSA-N 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- PTCWADDVLPYBBZ-UHFFFAOYSA-N tricyclopentylmethoxysilane Chemical compound C1CCCC1C(C1CCCC1)(O[SiH3])C1CCCC1 PTCWADDVLPYBBZ-UHFFFAOYSA-N 0.000 description 1
- ALVYUZIFSCKIFP-UHFFFAOYSA-N triethoxy(2-methylpropyl)silane Chemical compound CCO[Si](CC(C)C)(OCC)OCC ALVYUZIFSCKIFP-UHFFFAOYSA-N 0.000 description 1
- IOPAQHDEQBHWEB-UHFFFAOYSA-N trimethoxy-(2-methylcyclopentyl)silane Chemical compound CO[Si](OC)(OC)C1CCCC1C IOPAQHDEQBHWEB-UHFFFAOYSA-N 0.000 description 1
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- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明はポリプロピレンの製造方法に関し、詳しくは、重合後に特定の失活剤を使用する触媒失活工程を含むポリプロピレンの製造方法に関し、更に詳しくは、重合終了後の未反応モノマーおよび溶媒の回収を容易にし、これらを効率的に再利用することのできる触媒失活工程を含むポリプロピレンの製造方法に関する。 The present invention relates to a method for producing polypropylene, and more particularly, to a method for producing polypropylene including a catalyst deactivation step using a specific deactivator after polymerization, and more specifically, recovery of unreacted monomers and solvents after completion of polymerization. The present invention relates to a method for producing polypropylene, which includes a catalyst deactivation step that can be easily and efficiently reused.
ポリプロピレンは優れた機械的強度、電気絶縁性、食品衛生性、および光学特性等を有していることから様々な用途に用いられている。
ポリプロピレン樹脂の代表的な製造法としては、ヘキサンやヘプタン中で重合を行う溶媒法、プロピレン自身を溶媒として重合を行う塊状法、プロピレンガス中で重合を行う気相法、また、それらを組み合わせた方法、例えば、塊状法と気相法を組み合わせた方法などが有る。
Polypropylene is used in various applications because it has excellent mechanical strength, electrical insulation, food hygiene, optical properties, and the like.
Typical methods for producing a polypropylene resin include a solvent method in which polymerization is performed in hexane or heptane, a bulk method in which polymerization is performed using propylene itself as a solvent, a gas phase method in which polymerization is performed in propylene gas, or a combination thereof. There are methods, for example, a method combining a bulk method and a gas phase method.
これらの製造法では通常、重合工程の後に触媒の失活処理が行われる。従来の失活剤としては、メタノール、エタノール、プロパノール、イソプロパノール、ブタンジオールなどのアルコール類、酢酸メチル、酢酸エチル、酢酸ブチルなどの脂肪酸エステル類、エチレングリコール、プロピレングリコールなどのグリコール類、また、脂肪酸エステル類とグリコール類を合わせた脂肪酸グリコールエステル類など比較的分子量の低い化合物が用いられてきた。 In these production methods, the catalyst is usually deactivated after the polymerization step. Conventional quenchers include alcohols such as methanol, ethanol, propanol, isopropanol and butanediol, fatty acid esters such as methyl acetate, ethyl acetate and butyl acetate, glycols such as ethylene glycol and propylene glycol, and fatty acids. Compounds having a relatively low molecular weight such as fatty acid glycol esters in which esters and glycols are combined have been used.
しかし、溶媒法または塊状法によるポリプロピレンの製造において、ポリプロピレンスラリー中にこれらの失活剤を装入するという失活処理を行った場合、失活処理の後に回収したモノマーや溶媒中に失活剤が残存することがある。このような回収モノマーや回収溶媒を、例えば別の重合工程の原材料の一部または全部として利用すると、混入している失活剤の影響で該重合時の触媒活性の低下が引き起こされ、著しい場合は触媒活性が全く発現しなくなる。 However, in the production of polypropylene by the solvent method or the bulk method, when a deactivation treatment is performed in which these deactivators are charged into the polypropylene slurry, the deactivator is contained in the monomer or solvent recovered after the deactivation treatment. May remain. When such recovered monomer or recovered solvent is used as, for example, part or all of the raw material of another polymerization process, the catalytic activity during the polymerization is lowered due to the influence of the deactivator mixed therein, which is remarkable. No catalytic activity at all.
本発明は、モノマーおよび溶媒の回収の際に失活剤が混入し、これらの回収品を再利用したときに触媒活性が低下するという問題を抱えることのないポリプロピレン製造方法を提供することを課題とする。 It is an object of the present invention to provide a method for producing polypropylene which does not have a problem that a deactivator is mixed during the recovery of the monomer and the solvent and the catalytic activity is reduced when these recovered products are reused. And
本発明は、ポリプロピレンの重合工程後に特定の失活剤を用いた触媒失活工程を行うことにより、失活剤が混入することなくモノマーおよび溶媒を回収することを可能とし、上記の課題を解決するものである。 The present invention solves the above-mentioned problems by performing a catalyst deactivation step using a specific deactivation agent after the polymerization step of polypropylene, thereby allowing the monomer and solvent to be recovered without mixing the deactivation agent. To do.
すなわち本発明は、以下の(i)〜(iii)の事項に関する:
(i)有機アルミニウム化合物を含有する重合触媒の存在下で、溶媒法または塊状法によ
りプロピレンの単独重合またはプロピレンと他のオレフィンとの共重合を行う重合工程と、重合触媒の失活を行う失活工程とを有するポリプロピレンの製造方法であって、失活工程において失活剤として分子量が500以上の下記一般式[I]で表される化合物を、有
機アルミニウム化合物量に対して50〜1000モル%の範囲の量で添加することを特徴とするポリプロピレンの製造方法;
That is, the present invention relates to the following items (i) to (iii):
(I) a polymerization step in which propylene is homopolymerized or copolymerized with propylene and other olefins by a solvent method or a bulk method in the presence of a polymerization catalyst containing an organoaluminum compound, and a polymerization catalyst is deactivated. A method for producing polypropylene having an active step, wherein a compound represented by the following general formula [I] having a molecular weight of 500 or more is used as a deactivator in the deactivation step in an amount of 50 to 1000 mol with respect to the amount of the organoaluminum compound. A method for producing polypropylene, characterized in that it is added in an amount in the range of%;
R1−O−R−O−R2 ---------- [I]
(上記一般式[I]において、R1およびR2は、水素原子、炭素数1〜20のアルキル基
、炭素数6〜30のアリール基、炭素数1〜20のアシル基から選ばれ、相互に同一でも異なっていてもよい。Rはエーテル結合またはエステル結合を含んでいてもよい、炭素数2以上の炭化水素基を示す。)
(ii)失活剤が、下記一般式[II]で示される化合物であることを特徴とする(i)記載
のポリプロピレンの製造方法;
R 1 -O-R-O-R 2 ---------- [I]
(In the above general formula [I], R 1 and R 2 are selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an acyl group having 1 to 20 carbon atoms; And R represents a hydrocarbon group having 2 or more carbon atoms, which may contain an ether bond or an ester bond.)
(Ii) The method for producing polypropylene according to (i), wherein the quenching agent is a compound represented by the following general formula [II];
R1−O−[CH2−CH(R3)−O]k−R2 ---------- [II]
(上記一般式[II]において、R1、R2およびR3は、水素原子、炭素数1〜20のアル
キル基、炭素数6〜30のアリール基および炭素数1〜20のアシル基から選ばれ、相互に同一でも異なっていてもよい。kは平均繰り返し単位数を表わし、1〜100の範囲で
ある。)
(iii)失活剤が、下記一般式[III]で示される化合物であることを特徴とする(i)ま
たは(ii)記載のポリプロピレンの製造方法;
R 1 -O- [CH 2 -CH (R 3 ) -O] k -R 2 ---------- [II]
(In the general formula [II], R 1 , R 2 and R 3 are selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms and an acyl group having 1 to 20 carbon atoms. And may be the same or different from each other, k represents the average number of repeating units and is in the range of 1 to 100.)
(Iii) The method for producing polypropylene according to (i) or (ii), wherein the quenching agent is a compound represented by the following general formula [III]:
HO-(C2H4O)a-(C3H6O)b-(C2H4O)c-H ---------- [III]
(上記一般式[III]において、a,b,cは平均繰り返し単位数を表わし、各々1〜100の範囲である。)。
HO- (C 2 H 4 O) a- (C 3 H 6 O) b- (C 2 H 4 O) c -H ---------- [III]
(In the above general formula [III], a, b, and c represent the average number of repeating units, each ranging from 1 to 100).
本発明によれば、ポリプロピレンの製造を効率的に行うことができ、回収したモノマーおよび溶媒への失活剤の混入を簡便に抑制することが可能となり、回収したモノマーおよび溶媒を触媒失活のおそれなく再利用できるポリプロピレンの製造方法を提供することができる。 According to the present invention, it is possible to efficiently produce polypropylene, and it is possible to easily suppress the mixing of the deactivator into the recovered monomer and solvent, and the recovered monomer and solvent can be used for catalyst deactivation. A method for producing polypropylene that can be reused without fear can be provided.
以下、本発明に係る重合工程および失活工程、さらにその後に回収工程などについて順次説明する。
まず本発明に係る重合工程について、重合方法および使用される触媒などを説明する。
Hereinafter, the polymerization step and the deactivation step according to the present invention, and then the recovery step and the like will be sequentially described.
First, a polymerization method and a catalyst used in the polymerization step according to the present invention will be described.
本発明に係るプロピレンの重合は、プロピレンの単独重合またはプロピレンと他のオレフィンとの共重合である。
プロピレンと共重合する他のオレフィンとしては、エチレン、1−ブテン、1−オクテン、1−ヘキサデセン、1−エイコセンなどの直鎖状のオレフィン;3−メチル−1−ブテン、3−メチル−1−ペンテン、1−エチル−1−ペンテン、4−メチル−1−ペンテン、4−メチル−1−ヘキセン、4,4−ジメチル−1−ヘキセン、4,4−ジメチル−1−ペンテン、4−エチル−1−ヘキセン、3−エチル−1−ヘキセン、アリルナフタレン、アリルノルボルナン、スチレン、ジメチルスチレン類、ビニルナフタレン類、アリルトルエン類、アリルベンゼン、ビニルシクロヘキサン、ビニルシクロペンタン、ビニルシクロヘプタン、アリルトリアルキルシラン類などの分岐構造を有するオレフィンなどを用いることができ、これらの中ではエチレンが特に好ましく用いられる。
The propylene polymerization according to the present invention is propylene homopolymerization or copolymerization of propylene and other olefins.
Other olefins copolymerized with propylene include linear olefins such as ethylene, 1-butene, 1-octene, 1-hexadecene and 1-eicocene; 3-methyl-1-butene, 3-methyl-1- Pentene, 1-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl- 1-hexene, 3-ethyl-1-hexene, allylnaphthalene, allylnorbornane, styrene, dimethylstyrenes, vinylnaphthalenes, allyltoluenes, allylbenzene, vinylcyclohexane, vinylcyclopentane, vinylcycloheptane, allyltrialkylsilane Olefin having a branched structure such as Ethylene is particularly preferred.
なおこれらの重合については、単段重合でも多段重合でもよく、また連続法を用いてもバッチ法を用いてもよい。
本発明に係るプロピレンの重合方法は、不活性媒体を用いる溶媒重合法またはプロピレン自身を液状溶媒とする塊状重合法である。
These polymerizations may be single-stage polymerization or multi-stage polymerization, and a continuous method or a batch method may be used.
The propylene polymerization method according to the present invention is a solvent polymerization method using an inert medium or a bulk polymerization method using propylene itself as a liquid solvent.
プロピレンの重合を溶媒重合法にて行う場合、溶媒として用いる不活性炭化水素媒体としては、たとえばプロパン、ブタン、ペンタン、ヘキサン、ヘプタン、オクタン、デカン
、ドデカン、灯油などの脂肪族炭化水素;シクロペンタン、シクロヘキサン、メチルシクロペンタンなどの脂環族炭化水素;ベンゼン、トルエン、キシレンなどの芳香族炭化水素;エチレンクロリド、クロルベンゼンなどのハロゲン化炭化水素;あるいはこれらの混合物などが挙げられる。このうち、特に脂肪族炭化水素を用いることが好ましい。
In the case where propylene is polymerized by a solvent polymerization method, examples of the inert hydrocarbon medium used as a solvent include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane Alicyclic hydrocarbons such as cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene; or a mixture thereof. Of these, it is particularly preferable to use an aliphatic hydrocarbon.
プロピレンの重合は、一般的には−100〜200℃、好ましくは0〜100℃の範囲の温度で、また一般的には常圧〜100kg/cm2、好ましくは常圧〜50kg/cm2の範囲の圧力で行われる。 The polymerization of propylene is generally in the -100 to 200 ° C., preferably at a temperature in the range of 0 to 100 ° C., also generally normal pressure to 100 kg / cm 2, preferably atmospheric pressure to 50 kg / cm 2 Done in a range of pressures.
このような重合にて得られるプロピレン系重合体のメルトフローレート(測定条件:ASTM D−1238(230℃、2.16kg荷重))は、通常0.01〜200g/10min、好ましくは0.1〜120g/10minであり、極限粘度数(測定条件:135℃テトラリン中)は、通常0.3〜5.0dl/g、好ましくは0.5〜2.0dl/gである。また、分子量を所望の大きさにするために、水素を使用する公知の方法を利用して分子量の調節を行うことができる。 The melt flow rate (measurement conditions: ASTM D-1238 (230 ° C., 2.16 kg load)) of the propylene-based polymer obtained by such polymerization is usually 0.01 to 200 g / 10 min, preferably 0.1. The intrinsic viscosity (measuring condition: in 135 ° C. tetralin) is usually 0.3 to 5.0 dl / g, preferably 0.5 to 2.0 dl / g. Moreover, in order to make molecular weight into a desired magnitude | size, molecular weight can be adjusted using the well-known method using hydrogen.
本発明に係るプロピレンの重合は、有機アルミニウム化合物を含有する重合触媒の存在下で行われる。このような重合触媒としては、担持型チタン系触媒およびメタロセン触媒が挙げられる。 The polymerization of propylene according to the present invention is carried out in the presence of a polymerization catalyst containing an organoaluminum compound. Examples of such a polymerization catalyst include a supported titanium catalyst and a metallocene catalyst.
担持型チタン系触媒として、より具体的には、例えば(a)マグネシウム、チタン、ハロゲンおよび電子供与体を含有する固体状チタン触媒成分と、(b)有機アルミニウム化合物と、(c)電子供与体とを含むマグネシウム担持型チタン系触媒が挙げられる。また、上記(a)に代えて、マグネシウム化合物以外を担体として用いて調製した固体状チタン触媒成分(a’)を含む担持型チタン系触媒を挙げることもできる。 More specifically, as the supported titanium-based catalyst, for example, (a) a solid titanium catalyst component containing magnesium, titanium, halogen and an electron donor, (b) an organoaluminum compound, and (c) an electron donor. And magnesium-supported titanium-based catalysts. Further, in place of the above (a), a supported titanium-based catalyst containing a solid titanium catalyst component (a ') prepared using a carrier other than a magnesium compound can also be mentioned.
以下、本発明に係る担持型チタン系触媒の調製に使用される、マグネシウム化合物、マグネシウム化合物以外の担体、チタン、ハロゲン、電子供与体(以上aまたはa’の成分)、有機アルミニウム化合物(b)および電子供与体(c)について、順次説明する。 Hereinafter, magnesium compound, carrier other than magnesium compound, titanium, halogen, electron donor (component a or a ′), organoaluminum compound (b) used for the preparation of the supported titanium catalyst according to the present invention. The electron donor (c) will be described in turn.
固体状チタン触媒成分(a)の調製に用いられるマグネシウム化合物としては、還元能を有するマグネシウム化合物および還元能を有さないマグネシウム化合物を挙げることができる。 Examples of the magnesium compound used for the preparation of the solid titanium catalyst component (a) include a magnesium compound having a reducing ability and a magnesium compound not having a reducing ability.
還元能を有するマグネシウム化合物としては、マグネシウム−炭素結合またはマグネシウム−水素結合を有するマグネシウム化合物を挙げることができる。具体的にはジメチルマグネシウム、ジエチルマグネシウム、ジプロピルマグネシウム、ジブチルマグネシウム、ジアミルマグネシウム、ジヘキシルマグネシウム、ジデシルマグネシウム、エチル塩化マグネシウム、プロピル塩化マグネシウム、ブチル塩化マグネシウム、ヘキシル塩化マグネシウム、アミル塩化マグネシウム、ブチルエトキシマグネシウム、エチルブチルマグネシウム、ブチルマグネシウムハイドライドなどを挙げることができる。 Examples of the magnesium compound having a reducing ability include a magnesium compound having a magnesium-carbon bond or a magnesium-hydrogen bond. Specifically, dimethyl magnesium, diethyl magnesium, dipropyl magnesium, dibutyl magnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride, butyl ethoxy Examples thereof include magnesium, ethylbutylmagnesium, butylmagnesium hydride and the like.
還元能を有さないマグネシウム化合物としては、たとえば塩化マグネシウム、臭化マグネシウム、ヨウ化マグネシウム、フッ化マグネシウムなどのハロゲン化マグネシウム;メトキシ塩化マグネシウム、エトキシ塩化マグネシウム、イソプロポキシ塩化マグネシウム、ブトキシ塩化マグネシウム、オクトキシ塩化マグネシウムなどのアルコキシマグネシウムハライド;フェノキシ塩化マグネシウム、メチルフェノキシ塩化マグネシウムなどのアリロキシマグネシウムハライド;エトキシマグネシウム、イソプロポキシマグネシウム、ブトキシマグネシウム、n−オクトキシマグネシウム、2−エチルヘキソキシマグネシウムなどのアルコキシマグネシウム;フェノキシマグネシウム、ジメチルフェノキシマグネ
シウムなどのアリロキシマグネシウム;ラウリン酸マグネシウム、ステアリン酸マグネシウムなどのマグネシウムのカルボン酸塩等を挙げることができる。
Examples of magnesium compounds having no reducing ability include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, octoxy Alkoxymagnesium halides such as magnesium chloride; Allyloxymagnesium halides such as phenoxymagnesium chloride and methylphenoxymagnesium chloride; Alkoxymagnesiums such as ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, n-octoxymagnesium, 2-ethylhexoxymagnesium; Allyloxymagnes such as phenoxymagnesium and dimethylphenoxymagnesium Um; magnesium laurate, may be mentioned carboxylic acid salts of magnesium such as magnesium stearate.
これら還元能を有さないマグネシウム化合物は、還元能を有するマグネシウム化合物から誘導した化合物、または触媒成分の調製時に誘導した化合物であってもよい。還元能を有さないマグネシウム化合物を、還元能を有するマグネシウム化合物から誘導するには、たとえば還元能を有するマグネシウム化合物を、ポリシロキサン化合物、ハロゲン含有シラン化合物、ハロゲン含有アルミニウム化合物、エステル、アルコール、ハロゲン含有化合物、ケトンなどの活性な炭素−酸素結合を有する化合物と接触させればよい。 These magnesium compounds having no reducing ability may be compounds derived from a magnesium compound having reducing ability, or compounds derived during the preparation of the catalyst component. In order to derive a magnesium compound having no reducing ability from a magnesium compound having a reducing ability, for example, a magnesium compound having a reducing ability is converted into a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, a halogen, and the like. What is necessary is just to make it contact with the compound which has active carbon-oxygen bonds, such as a containing compound and a ketone.
本発明では、上述した以外にも多くのマグネシウム化合物が使用できるが、最終的に得られる固体状チタン触媒成分(a)中において、ハロゲン含有マグネシウム化合物の形をとることが好ましく、従ってハロゲンを含まないマグネシウム化合物を用いる場合には、触媒成分を調製する過程でハロゲン含有化合物と接触反応させることが好ましい。 In the present invention, many magnesium compounds can be used in addition to those described above. However, in the finally obtained solid titanium catalyst component (a), it is preferable to take the form of a halogen-containing magnesium compound, and thus a halogen is contained. In the case of using a magnesium compound that is not present, it is preferable to cause a contact reaction with a halogen-containing compound in the course of preparing the catalyst component.
マグネシウム化合物としては還元能を有さないマグネシウム化合物が好ましく、ハロゲン含有マグネシウム化合物がさらに好ましく、塩化マグネシウム、アルコキシ塩化マグネシウム、アリロキシ塩化マグネシウムが特に好ましい。 As the magnesium compound, a magnesium compound having no reducing ability is preferable, a halogen-containing magnesium compound is more preferable, and magnesium chloride, alkoxy magnesium chloride, and allyloxy magnesium chloride are particularly preferable.
本発明に係る担持型チタン系触媒には、前記のマグネシウム化合物以外を担体として用いて調製した固体状チタン触媒成分(a’)を用いることもできる。マグネシウム化合物以外の化合物としては、無機または有機の化合物であって、顆粒状ないしは微粒子状の固体を例示することができる。 In the supported titanium-based catalyst according to the present invention, a solid titanium catalyst component (a ′) prepared using a carrier other than the above magnesium compound can also be used. Examples of the compound other than the magnesium compound include inorganic or organic compounds and granular or fine particle solids.
固体状チタン触媒成分(a’)の担体として用いる無機化合物としては、多孔質酸化物、粘土、粘土鉱物またはイオン交換性層状化合物が好ましい。
多孔質酸化物として、具体的にはSiO2、Al2O3、MgO、ZrO、TiO2、B2
O3、CaO、ZnO、BaO、ThO2、SnO2など、またはこれらを含む複合物もし
くは混合物を、例えば天然または合成ゼオライト、SiO2−MgO、SiO2−Al2O3、SiO2−TiO2、SiO2−V2O5、SiO2−Cr2O3、SiO2−TiO2−MgOなどを使用することができる。これらのうち、SiO2および/またはAl2O3を主成分
とするものが好ましい。
As the inorganic compound used as the carrier for the solid titanium catalyst component (a ′), a porous oxide, clay, clay mineral, or ion-exchangeable layered compound is preferable.
Specific examples of the porous oxide include SiO 2 , Al 2 O 3 , MgO, ZrO, TiO 2 and B 2.
O 3 , CaO, ZnO, BaO, ThO 2 , SnO 2, etc., or composites or mixtures containing these, eg natural or synthetic zeolite, SiO 2 —MgO, SiO 2 —Al 2 O 3 , SiO 2 —TiO 2. SiO 2 —V 2 O 5 , SiO 2 —Cr 2 O 3 , SiO 2 —TiO 2 —MgO, or the like can be used. Of these, those containing SiO 2 and / or Al 2 O 3 as main components are preferred.
なお、上記無機酸化物は、少量のNa2CO3、K2CO3、CaCO3、MgCO3、Na2SO4、Al2(SO4)3、BaSO4、KNO3、Mg(NO3)2、Al(NO3)3、N
a2O、K2O、Li2Oなどの炭酸塩、硫酸塩、硝酸塩、酸化物成分を含有していても差
し支えない。
Note that the inorganic oxide includes a small amount of Na 2 CO 3 , K 2 CO 3 , CaCO 3 , MgCO 3 , Na 2 SO 4 , Al 2 (SO 4 ) 3 , BaSO 4 , KNO 3 , Mg (NO 3 ). 2 , Al (NO 3 ) 3 , N
It may contain carbonates, sulfates, nitrates and oxide components such as a 2 O, K 2 O and Li 2 O.
このような多孔質酸化物は、種類および製法によりその性状は異なるが、本発明に好ましく用いられる担体は、粒径が10〜300μm、好ましくは20〜200μmであって、比表面積が50〜1000m2/g、好ましくは100〜700m2/gの範囲にあり、細孔容積が0.3〜3.0cm3/gの範囲にあることが望ましい。このような担体は、
必要に応じて100〜1000℃、好ましくは150〜700℃で焼成して使用される。
Such porous oxides have different properties depending on the type and production method, but the carrier preferably used in the present invention has a particle size of 10 to 300 μm, preferably 20 to 200 μm, and a specific surface area of 50 to 1000 m. 2 / g, preferably in the range of 100 to 700 m 2 / g and the pore volume in the range of 0.3 to 3.0 cm 3 / g. Such carriers are
If necessary, it is baked at 100 to 1000 ° C, preferably 150 to 700 ° C.
本発明で用いられる粘土は、通常粘土鉱物を主成分として構成される。また、本発明で用いられるイオン交換性層状化合物は、イオン結合などによって構成される面が互いに弱い結合力で平行に積み重なった結晶構造を有する化合物であり、含有するイオンが交換可能なものである。大部分の粘土鉱物はイオン交換性層状化合物である。また、これらの粘土、粘土鉱物、イオン交換性層状化合物としては、天然産のものに限らず、人工合成物を使用することもできる。 The clay used in the present invention is usually composed mainly of clay minerals. The ion-exchangeable layered compound used in the present invention is a compound having a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with each other with a weak binding force, and the contained ions can be exchanged. . Most clay minerals are ion-exchangeable layered compounds. In addition, these clays, clay minerals, and ion-exchange layered compounds are not limited to natural products, and artificial synthetic products can also be used.
また、粘土、粘土鉱物またはイオン交換性層状化合物として、粘土、粘土鉱物、また、六方細密パッキング型、アンチモン型、CdCl2型、CdI2型などの層状の結晶構造を有するイオン結晶性化合物などを例示することができる。 In addition, as clay, clay mineral, or ion-exchangeable layered compound, clay, clay mineral, ionic crystalline compound having a layered crystal structure such as hexagonal fine packing type, antimony type, CdCl 2 type, CdI 2 type, etc. It can be illustrated.
このような粘土、粘土鉱物としては、カオリン、ベントナイト、木節粘土、ガイロメ粘土、アロフェン、ヒシンゲル石、パイロフィライト、ウンモ群、モンモリロナイト群、バーミキュライト、リョクデイ石群、パリゴルスカイト、カオリナイト、ナクライト、ディッカイト、ハロイサイトなどが挙げられ、イオン交換性層状化合物としては、α−Zr(HAsO4)2・H2O、α−Zr(HPO4)2、α−Zr(KPO4)2・3H2O、α−Ti(HPO4)2、α−Ti(HAsO4)2・H2O、α−Sn(HPO4)2・H2O、γ−Zr(HPO4)2、γ−Ti(HPO4)2、γ−Ti(NH4PO4)2・H2Oなどの多価金属の結晶性酸性塩などが挙げられる。 Examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, nacrite, dickite And ionizable layered compounds include α-Zr (HAsO4) 2 .H 2 O, α-Zr (HPO 4 ) 2 , α-Zr (KPO 4 ) 2 .3H 2 O, α -Ti (HPO 4 ) 2 , α-Ti (HAsO 4 ) 2 .H 2 O, α-Sn (HPO 4 ) 2 .H 2 O, γ-Zr (HPO 4 ) 2 , γ-Ti (HPO 4 ) 2 , Examples thereof include crystalline acidic salts of polyvalent metals such as γ-Ti (NH 4 PO 4 ) 2 .H 2 O.
このような粘土、粘土鉱物またはイオン交換性層状化合物は、水銀圧入法で測定した半径20Å以上の細孔容積が0.1cc/g以上のものが好ましく、0.3〜5cc/gのものが特に好ましい。ここで、細孔容積は、水銀ポロシメーターを用いた水銀圧入法により、細孔半径20〜3×104Åの範囲について測定される。 Such a clay, clay mineral, or ion-exchange layered compound preferably has a pore volume of 0.1 cc / g or more and a diameter of 0.3 to 5 cc / g measured by mercury porosimetry. Particularly preferred. Here, the pore volume is measured in the range of pore radius of 20 to 3 × 10 4 Å by mercury porosimetry using a mercury porosimeter.
半径20Å以上の細孔容積が0.1cc/gより小さいものを担体として用いた場合には、高い重合活性が得られにくい傾向がある。
本発明で用いられる粘土、粘土鉱物には、化学処理を施すことも好ましい。化学処理としては、表面に付着している不純物を除去する表面処理、粘土の結晶構造に影響を与える処理など、何れも使用できる。化学処理として具体的には、酸処理、アルカリ処理、塩類処理、有機物処理などが挙げられる。酸処理は、表面の不純物を取り除くほか、結晶構造中のAl、Fe、Mgなどの陽イオンを溶出させることによって表面積を増大させる。アルカリ処理では粘土の結晶構造が破壊され、粘土の構造の変化をもたらす。また、塩類処理、有機物処理では、イオン複合体、分子複合体、有機誘導体などを形成し、表面積や層間距離を変えることができる。
When a carrier having a pore volume with a radius of 20 mm or more and smaller than 0.1 cc / g is used as a carrier, high polymerization activity tends to be difficult to obtain.
The clay and clay mineral used in the present invention are preferably subjected to chemical treatment. As the chemical treatment, any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the crystal structure of clay can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic matter treatment. In addition to removing impurities on the surface, the acid treatment increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. In the salt treatment and the organic matter treatment, an ion complex, a molecular complex, an organic derivative, or the like can be formed, and the surface area or interlayer distance can be changed.
本発明で用いられるイオン交換性層状化合物は、イオン交換性を利用し、層間の交換性イオンを別の大きな嵩高いイオンと交換することにより、層間が拡大した状態の層状化合物であってもよい。このような嵩高いイオンは、層状構造を支える支柱的な役割を担っており、通常、ピラーと呼ばれる。また、このように層状化合物の層間に別の物質を導入することをインターカレーションという。インターカレーションするゲスト化合物としては、TiCl4、ZrCl4などの陽イオン性無機化合物、Ti(OR)4、Zr(OR)4、PO(OR)3、B(OR)3などの金属アルコキシド(Rは炭化水素基など)、[Al13O4(OH)24]7+、[Zr4(OH)14]2+、[Fe3O(OCOCH3)6]+などの金属水酸化物イオンなどが挙げられる。これらの化合物は単独でまたは2種以上組み合わせて用いられる。また、これらの化合物をインターカレーションする際に、Si(OR)4、
Al(OR)3、Ge(OR)4などの金属アルコキシド(Rは炭化水素基など)などを加水分解して得た重合物、SiO2などのコロイド状無機化合物などを共存させることもで
きる。また、ピラーとしては、上記金属水酸化物イオンを層間にインターカレーションした後に加熱脱水することにより生成する酸化物などが挙げられる。
The ion-exchangeable layered compound used in the present invention may be a layered compound in a state where the layers are expanded by exchanging the exchangeable ions between the layers with other large and bulky ions using the ion-exchange property. . Such bulky ions play a role of supporting pillars to support the layered structure and are usually called pillars. Moreover, introducing another substance between the layers of the layered compound in this way is called intercalation. Examples of guest compounds to be intercalated include cationic inorganic compounds such as TiCl 4 and ZrCl 4 , metal alkoxides such as Ti (OR) 4 , Zr (OR) 4 , PO (OR) 3 , and B (OR) 3 ( R is a hydrocarbon group), metal hydroxide ions such as [Al 13 O 4 (OH) 24 ] 7+ , [Zr 4 (OH) 14 ] 2+ , [Fe 3 O (OCOCH 3 ) 6 ] + Etc. These compounds are used alone or in combination of two or more. In addition, when intercalating these compounds, Si (OR) 4 ,
A polymer obtained by hydrolyzing a metal alkoxide (R is a hydrocarbon group or the like) such as Al (OR) 3 or Ge (OR) 4, a colloidal inorganic compound such as SiO 2, etc. may be allowed to coexist. Examples of the pillar include oxides generated by heat dehydration after intercalation of the metal hydroxide ions between layers.
本発明で用いられる粘土、粘土鉱物、イオン交換性層状化合物は、そのまま用いてもよく、またボールミル、ふるい分けなどの処理を行った後に用いてもよい。また、新たに水を添加吸着させ、あるいは加熱脱水処理した後に用いてもよい。さらに、単独で用いても、2種以上を組み合わせて用いてもよい。これらのうち、好ましいものは粘土または粘土鉱物であり、特に好ましいものはモンモリロナイト、バーミキュライト、ペクトライト、
テニオライトおよび合成雲母である。
The clay, clay mineral, and ion-exchangeable layered compound used in the present invention may be used as they are, or may be used after a treatment such as ball milling or sieving. Further, it may be used after water is newly added and adsorbed, or after heat dehydration treatment. Furthermore, you may use individually or in combination of 2 or more types. Of these, preferred are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, pectolite,
Teniolite and synthetic mica.
固体状チタン触媒成分(a’)の担体として用いる有機化合物としては、粒径が10〜300μmの範囲にある顆粒状ないしは微粒子状固体を挙げることができる。より具体的には、エチレン、プロピレン、1−ブテン、4−メチル−1−ペンテンなどの炭素原子数が2〜14のα−オレフィンを主成分として生成される(共)重合体またはビニルシクロヘキサン、スチレンを主成分として生成される(共)重合体ならびにそれらの変成体を、一例としてはスチレン−ジビニルベンゼン共重合体を挙げることができる。 Examples of the organic compound used as the carrier for the solid titanium catalyst component (a ′) include granular or fine particle solids having a particle size in the range of 10 to 300 μm. More specifically, a (co) polymer or vinylcyclohexane produced mainly from an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, Examples of (co) polymers produced from styrene as a main component and their modified products include styrene-divinylbenzene copolymers.
固体状チタン触媒成分(a)または(a’)の調製の際に用いられるチタンとしては、例えば次式(II)で示される4価のチタン化合物が好ましい。
Ti(OR)gX4-g …(II)
(式(II)中、Rは炭化水素基、Xはハロゲン原子、0≦g≦4である。)
具体的にはTiCl4、TiBr4、TiI4などのテトラハロゲン化チタン;Ti(OCH3)Cl3、Ti(OC2H5)Cl3、Ti(O−n−C4H9)Cl3、Ti(OC2H5)Br3、Ti(O−iso−C4H9)Br3などのトリハロゲン化アルコキシチタン;Ti(OCH3)2Cl2、Ti(OC2H5)2Cl2、Ti(O−C4H9)2Cl2、Ti(OC2H5)2Br2などのジハロゲン化ジアルコキシチタン;Ti(OCH3)3Cl、Ti(OC2H5)3Cl、Ti(O−n−C4H9)3Cl、Ti(OC2H5)3Brなどのモノハロゲン化トリアルコキシチタン
;Ti(OCH3)4、Ti(OC2H5)4、Ti(O−n−C4H9)4、Ti(O−iso−C4H9)4、Ti(O−2−エチルヘキシル)4などのテトラアルコキシチタン等が挙げられる。
As the titanium used in the preparation of the solid titanium catalyst component (a) or (a ′), for example, a tetravalent titanium compound represented by the following formula (II) is preferable.
Ti (OR) g X 4-g (II)
(In the formula (II), R is a hydrocarbon group, X is a halogen atom, and 0 ≦ g ≦ 4.)
Specifically, titanium tetrahalides such as TiCl 4 , TiBr 4 , and TiI 4 ; Ti (OCH 3 ) Cl 3 , Ti (OC 2 H 5 ) Cl 3 , Ti (On-C 4 H 9 ) Cl 3 , Ti (OC 2 H 5 ) Br 3 , Ti (O-iso-C 4 H 9 ) Br 3 and other trihalogenated alkoxytitanium; Ti (OCH 3 ) 2 Cl 2 , Ti (OC 2 H 5 ) 2 Cl 2 , Di (halogenated dialkoxytitanium) such as Ti (O—C 4 H 9 ) 2 Cl 2 , Ti (OC 2 H 5 ) 2 Br 2 ; Ti (OCH 3 ) 3 Cl, Ti (OC 2 H 5 ) 3 Cl , Ti (O-n-C 4 H 9) 3 Cl, Ti (OC 2 H 5) 3 monohalogenated trialkoxy titanium such as Br; Ti (OCH 3) 4 , Ti (OC 2 H 5) 4, Ti (O-n-C 4 H 9) 4, Ti (O-iso-C 4 H 9) 4, Ti tetraalkoxy titanium is levator such (O-2-ethylhexyl) 4 It is.
これらの中ではハロゲン含有チタン化合物が好ましく、さらにテトラハロゲン化チタンが好ましく、特に四塩化チタンが好ましい。チタン化合物は、炭化水素化合物またはハロゲン化炭化水素化合物などに希釈して用いることもできる。 Among these, halogen-containing titanium compounds are preferable, titanium tetrahalides are more preferable, and titanium tetrachloride is particularly preferable. The titanium compound can be diluted with a hydrocarbon compound or a halogenated hydrocarbon compound.
固体状チタン触媒成分(a)または(a’)の調製の際に用いられる電子供与体としては、たとえばアルコール、フェノール、ケトン、アルデヒド、有機酸または無機酸のエステル、有機酸ハライド、エーテル、酸アミド、酸無水物、アンモニア、アミン、ニトリル、イソシアネート、含窒素環状化合物、含酸素環状化合物などが挙げられる。 Examples of the electron donor used in the preparation of the solid titanium catalyst component (a) or (a ′) include alcohols, phenols, ketones, aldehydes, esters of organic acids or inorganic acids, organic acid halides, ethers, acids. Examples thereof include amides, acid anhydrides, ammonia, amines, nitriles, isocyanates, nitrogen-containing cyclic compounds, and oxygen-containing cyclic compounds.
より具体的には、メタノール、エタノール、プロパノール、ペンタノール、ヘキサノール、オクタノール、2−エチルヘキサノール、ドデカノール、オクタデシルアルコール、オレイルアルコール、ベンジルアルコール、フェニルエチルアルコール、クミルアルコール、イソプロピルアルコール、イソプロピルベンジルアルコールなどの炭素数1〜18のアルコール類;フェノール、クレゾール、キシレノール、エチルフェノール、プロピルフェノール、ノニルフェノール、クミルフェノール、ナフトールなどの低級アルキル基を有してもよい炭素数6〜20のフェノール類;アセトン、メチルエチルケトン、メチルイソブチルケトン、アセトフェノン、ベンゾフェノン、アセチルアセトン、ベンゾキノンなどの炭素数3〜15のケトン類;アセトアルデヒド、プロピオンアルデヒド、オクチルアルデヒド、ベンズアルデヒド、トルアルデヒド、ナフトアルデヒドなどの炭素数2〜15のアルデヒド類;ギ酸メチル、酢酸メチル、酢酸エチル、酢酸ビニル、酢酸プロピル、酢酸オクチル、酢酸シクロヘキシル、プロピオン酸エチル、酪酸メチル、吉草酸エチル、クロル酢酸メチル、ジクロル酢酸エチル、メタクリル酸メチル、クロトン酸エチル、シクロヘキサンカルボン酸エチル、安息香酸メチル、安息香酸エチル、安息香酸プロピル、安息香酸ブチル、安息香酸オクチル、安息香酸シクロヘキシル、安息香酸フェニル、安息香酸ベンジル、トルイル酸メチル、トルイル酸エチル、トルイル酸アミル、エチル安息香酸エチル、アニス酸メチル、マレイン酸n−ブチル、メチルマロン酸ジイソブチル、シクロヘキセンカルボン酸ジn−ヘキシル、ナジック酸ジエチル、テトラヒドロフタル酸ジイソプロピル、フタル酸ジエチル、フタル酸ジイソブチル、フタル酸ジn−ブチル、フタル酸ジ2
−エチルヘキシル、γ−ブチロラクトン、δ−バレロラクトン、クマリン、フタリド、炭酸エチルなどの炭素数2〜30の有機酸エステル;アセチルクロリド、ベンゾイルクロリド、トルイル酸クロリド、アニス酸クロリドなどの炭素数2〜15の酸ハライド類;メチルエーテル、エチルエーテル、イソプロピルエーテル、ブチルエーテル、アミルエーテル、アニソール、ジフェニルエチルエポキシ−p−メンタンなどの炭素数2〜20のエーテル類;酢酸アミド、安息香酸アミド、トルイル酸アミドなどの酸アミド類;無水酢酸、無水フタル酸、無水安息香酸などの酸無水物;メチルアミン、エチルアミン、ジメチルアミン、ジエチルアミン、エチレンジアミン、テトラメチレンジアミン、ヘキサメチレンジアミン、トリブチルアミン、トリベンジルアミンなどのアミン類;アセトニトリル、ベンゾニトリル、トルニトリルなどのニトリル類;ピロール、メチルピロール、ジメチルピロールなどのピロール類、ピロリン、ピロリジン、インドール、ピリジン、メチルピリジン、エチルピリジン、プロピルピリジン、ジメチルピリジン、エチルメチルピリジン、トリメチルピリジン、フェニルピリジン、ベンジルピリジン、塩化ピリジンなどのピリジン類、ピペリジン類、キノリン類、イソキノリン類などの含窒素環状化合物;テトラヒドロフラン、1,4−シネオール、1,8−シネオール、ピノールフラン、メチルフラン、ジメチルフラン、ジフェニルフラン、ベンゾフラン、クマラン、フタラン、テトラヒドロピラン、ピラン、ジヒドロピランなどの環状含酸素化合物等が挙げることができる。
More specifically, methanol, ethanol, propanol, pentanol, hexanol, octanol, 2-ethylhexanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, isopropylbenzyl alcohol, etc. Alcohols having 1 to 18 carbon atoms; phenols having 6 to 20 carbon atoms which may have a lower alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol, naphthol; acetone Ketones having 3 to 15 carbon atoms such as methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, acetylacetone, and benzoquinone; C2-15 aldehydes such as cetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, propionic acid Ethyl, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, Cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl benzoate, methyl anisate, n-butyl maleate, methylmalon Diisobutyl, cyclohexene carboxylic di n- hexyl, nadic diethyl, tetrahydrophthalic acid diisopropyl, diethyl phthalate, diisobutyl phthalate, di n- butyl phthalate, di 2
-C2-C30 organic acid ester such as ethylhexyl, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethyl carbonate; C2-C15 such as acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride Acid halides; methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, anisole, diphenylethyl epoxy-p-menthane and other ethers having 2 to 20 carbon atoms; acetic acid amide, benzoic acid amide, toluic acid amide, etc. Acid amides; acid anhydrides such as acetic anhydride, phthalic anhydride, benzoic anhydride; methylamine, ethylamine, dimethylamine, diethylamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, tributylamine, tributylamine Amines such as benzylamine; Nitriles such as acetonitrile, benzonitrile and tolunitrile; pyrroles such as pyrrole, methylpyrrole and dimethylpyrrole, pyrroline, pyrrolidine, indole, pyridine, methylpyridine, ethylpyridine, propylpyridine, dimethylpyridine, Pyridines such as ethylmethylpyridine, trimethylpyridine, phenylpyridine, benzylpyridine, pyridine chloride, nitrogen-containing cyclic compounds such as piperidines, quinolines, isoquinolines; tetrahydrofuran, 1,4-cineole, 1,8-cineole, pino Examples include cyclic oxygenates such as rufuran, methylfuran, dimethylfuran, diphenylfuran, benzofuran, coumaran, phthalane, tetrahydropyran, pyran, dihydropyran. It is possible.
また上記の有機酸エステルとしては、多価カルボン酸エステルを特に好ましい例として挙げることができる。このような多価カルボン酸エステルとしては、具体的には、コハク酸ジエチル、コハク酸ジブチル、メチルコハク酸ジエチル、α−メチルグルタル酸ジイソブチル、メチルマロン酸ジエチル、エチルマロン酸ジエチル、イソプロピルマロン酸ジエチル、ブチルマロン酸ジエチル、フェニルマロン酸ジエチル、ジエチルマロン酸ジエチル、ジブチルマロン酸ジエチル、マレイン酸モノオクチル、マレイン酸ジオクチル、マレイン酸ジブチル、ブチルマレイン酸ジブチル、フチルマレイン酸ジエチル、β−メチルグルタル酸ジイソプロピル、エチルコハク酸ジアルリル、フマル酸ジ−2−エチルヘキシル、イタコン酸ジエチル、シトラコン酸ジオクチルなどの脂肪族ポリカルボン酸エステル;1,2−シクロヘキサンカルボン酸ジエチル、1,2−シクロヘキサンカルボン酸ジイソブチル、テトラヒドロフタル酸ジエチル、ナジック酸ジエチルなどの脂環族ポリカルボン酸エステル;フタル酸モノエチル、フタル酸ジメチル、フタル酸メチルエチル、フタル酸モノイソブチル、フタル酸ジエチル、フタル酸エチルイソブチル、フタル酸ジn−プロピル、フタル酸ジイソプロピル、フタル酸ジn−ブチル、フタル酸ジイソブチル、フタル酸ジn−ヘプチル、フタル酸ジ−2−エチルヘキシル、フタル酸ジn−オクチル、フタル酸ジネオペンチル、フタル酸ジデシル、フタル酸ベンジルブチル、フタル酸ジフェニル、ナフタリンジカルボン酸ジエチル、ナフタリンジカルボン酸ジブチル、トリメリット酸トリエチル、トリメリット酸ジブチルなどの芳香族ポリカルボン酸エステル等が挙げられる。 Moreover, as said organic acid ester, polyvalent carboxylic acid ester can be mentioned as a particularly preferable example. Specific examples of such polycarboxylic acid esters include diethyl succinate, dibutyl succinate, diethyl methyl succinate, diisobutyl α-methylglutarate, diethyl methylmalonate, diethyl ethylmalonate, diethyl isopropylmalonate, Diethyl butylmalonate, diethyl phenylmalonate, diethyl diethylmalonate, diethyl dibutylmalonate, monooctyl maleate, dioctyl maleate, dibutyl maleate, dibutyl butyl maleate, diethyl butyl maleate, diisopropyl β-methylglutarate, ethyl succinate Aliphatic polycarboxylic acid esters such as diallyl acid, di-2-ethylhexyl fumarate, diethyl itaconate, dioctyl citraconic acid; diethyl 1,2-cyclohexanecarboxylate, 1,2- Alicyclic polycarboxylic acid esters such as diisobutyl cyclohexanecarboxylate, diethyl tetrahydrophthalate, diethyl nadic acid; monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, monoisobutyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, Di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, dineopentyl phthalate, phthalic acid Examples include aromatic polycarboxylic acid esters such as didecyl, benzylbutyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitic acid, and dibutyl trimellitic acid. .
本発明では、上記の中ではカルボン酸エステルを用いることが好ましく、特に多価カルボン酸エステル、とりわけフタル酸エステル類を用いることが好ましい。
固体状チタン触媒成分(a)または(a’)において、ハロゲン/チタン(原子比)は2〜200、好ましくは4〜100であり、前記電子供与体/チタン(モル比)は0.01〜200、好ましくは0.01〜100である。また固体状チタン触媒成分(a)においては、マグネシウム/チタン(原子比)は1〜100、好ましくは2〜50であることが望ましい。
In the present invention, carboxylic acid esters are preferably used in the above, and polyvalent carboxylic acid esters, particularly phthalic acid esters are particularly preferably used.
In the solid titanium catalyst component (a) or (a ′), the halogen / titanium (atomic ratio) is 2-200, preferably 4-100, and the electron donor / titanium (molar ratio) is 0.01- 200, preferably 0.01-100. In the solid titanium catalyst component (a), the magnesium / titanium (atomic ratio) is 1 to 100, preferably 2 to 50.
本発明に係る担持型チタン系触媒には、上記のような固体状チタン触媒成分(a)または(a’)とともに、有機アルミニウム化合物(b)が含まれる。
前記の有機アルミニウム化合物としては、たとえば下記式(III)で示される化合物が
好ましい;
R1 mAlX3-m …(III)
(式(III)中、R1は炭化水素基、Xはハロゲン、mは好ましくは0<m<3である。)。
The supported titanium-based catalyst according to the present invention contains the organoaluminum compound (b) together with the solid titanium catalyst component (a) or (a ′) as described above.
As the organoaluminum compound, for example, a compound represented by the following formula (III) is preferable;
R 1 m AlX 3-m (III)
(In Formula (III), R 1 is a hydrocarbon group, X is a halogen, and m is preferably 0 <m <3).
このような有機アルミニウム化合物としては、より具体的には、トリエチルアルミニウム、トリブチルアルミニウムなどのトリアルキルアルミニウム;トリイソプレニルアルミニウムなどのトリアルケニルアルミニウム;ジエチルアルミニウムクロリド、ジブチルアルミニウムクロリド、ジエチルアルミニウムブロミドなどのジアルキルアルミニウムハライド;エチルアルミニウムセスキクロリド、ブチルアルミニウムセスキクロリド、エチルアルミニウムセスキブロミドなどのアルキルアルミニウムセスキハライド;エチルアルミニウムジクロリド、プロピルアルミニウムジクロリド、ブチルアルミニウムジブロミドなどのアルキルアルミニウムジハライドなどの部分的にハロゲン化されたアルキルアルミニウム等があげられる。 More specifically, the organoaluminum compound includes trialkylaluminum such as triethylaluminum and tributylaluminum; trialkenylaluminum such as triisoprenylaluminum; dialkyl such as diethylaluminum chloride, dibutylaluminum chloride and diethylaluminum bromide. Alkyl halides; alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide; partially halogenated such as alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide And alkylaluminum.
これらの中では特にトリアルキルアルミニウムが好ましく用いられる。
本発明に係る担持型チタン系触媒には、上記のような固体状チタン触媒成分(a)または(a’)および有機金属化合物(b)とともに、電子供与体(c)が含まれる。この電子供与体(c)としては、好ましくは有機ケイ素化合物(c−1)または複数の原子を介して存在する2個以上のエーテル結合を有する化合物(以下、ポリエーテル化合物という場合もある)(c−2)が用いられる。
Of these, trialkylaluminum is particularly preferably used.
The supported titanium-based catalyst according to the present invention includes an electron donor (c) together with the solid titanium catalyst component (a) or (a ′) and the organometallic compound (b) as described above. The electron donor (c) is preferably an organosilicon compound (c-1) or a compound having two or more ether bonds existing through a plurality of atoms (hereinafter sometimes referred to as a polyether compound) ( c-2) is used.
担持型チタン系触媒に用いられる有機ケイ素化合物(c−1)は、下記式(IV)で示される。
Ra nSi(ORb)4-n …(IV)
(式(IV)中、nは1、2または3であり、nが1のときRaは2級または3級の炭化水
素基であり、nが2または3のときRaの少なくとも1つは2級または3級の炭化水素基
であり、Raは同一であっても異なっていてもよく、Rbは炭素数1〜4の炭化水素基であって、4−nが2または3であるときRbは同一であっても異なっていてもよい。)
上記式(IV)で示される有機ケイ素化合物(c−1)は、nが1である場合には、シクロペンチルトリメトキシシラン、2−メチルシクロペンチルトリメトキシシラン、2,3−ジメチルシクロペンチルトリメトキシシラン、シクロペンチルトリエトキシシラン、iso−ブチルトリエトキシシラン、t−ブチルトリエトキシシラン、シクロヘキシルトリメトキシシラン、シクロヘキシルトリエトキシシラン、2−ノルボルナントリメトキシシラン、2−ノルボルナントリエトキシシランなどのトリアルコキシシラン類を挙げることができる。
The organosilicon compound (c-1) used for the supported titanium-based catalyst is represented by the following formula (IV).
R a n Si (OR b) 4-n ... (IV)
(In the formula (IV), n is 1, 2 or 3; when n is 1, R a is a secondary or tertiary hydrocarbon group; and when n is 2 or 3, at least one of R a Is a secondary or tertiary hydrocarbon group, R a may be the same or different, R b is a hydrocarbon group having 1 to 4 carbon atoms, and 4-n is 2 or 3 And R b may be the same or different.)
When n is 1, the organosilicon compound (c-1) represented by the above formula (IV) is cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane, Examples of trialkoxysilanes such as cyclopentyltriethoxysilane, iso-butyltriethoxysilane, t-butyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, and 2-norbornanetriethoxysilane be able to.
上記(IV)においてnが2である場合には、ジシクロペンチルジエトキシシラン、t−ブチルメチルジメトキシシラン、t−ブチルメチルジエトキシシラン、t−アミルメチルジエトキシシラン、ジシクロヘキシルジメトキシシラン、シクロヘキシルメチルジメトキシシラン、シクロヘキシルメチルジエトキシシラン、2−ノルボルナンメチルジメトキシシランなどのジアルコキシシラン類が挙げられる。 In the above (IV), when n is 2, dicyclopentyldiethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxy Examples thereof include dialkoxysilanes such as silane, cyclohexylmethyldiethoxysilane, and 2-norbornanemethyldimethoxysilane.
上記(IV)においてnが3である場合には、トリシクロペンチルメトキシシラン、トリシクロペンチルエトキシシラン、ジシクロペンチルメチルメトキシシラン、ジシクロペンチルエチルメトキシシラン、ジシクロペンチルメチルエトキシシラン、シクロペンチルジメチルメトキシシラン、シクロペンチルジエチルメトキシシラン、シクロペンチルジメチルエトキシシラン、トリメチルメトキシシランなどのモノアルコキシシラン類などが挙げられる。 In the above (IV), when n is 3, tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxy And monoalkoxysilanes such as silane, cyclopentyldimethylethoxysilane, and trimethylmethoxysilane.
これらの中ではジメトキシシラン類が好ましく、具体的に、ジシクロペンチルジメトキシシラン、ジ−t−ブチルジメトキシシラン、ジ(2−メチルシクロペンチル)ジメトキ
シシラン、ジ(3−メチルシクロペンチル)ジメトキシシラン、ジ−t−アミルジメトキシシランなどが好ましい。
Among these, dimethoxysilanes are preferable, and specifically, dicyclopentyldimethoxysilane, di-t-butyldimethoxysilane, di (2-methylcyclopentyl) dimethoxysilane, di (3-methylcyclopentyl) dimethoxysilane, di-t. -Amyldimethoxysilane is preferred.
担持型チタン系触媒に用いられる前記ポリエーテル化合物(c−2)では、エーテル結合間に存在する原子は炭素、ケイ素、酸素、硫黄、リンおよびホウ素からなる群から選ばれる1種以上であり、原子数は2以上である。これらのうちエーテル結合間の原子に比較的嵩高い置換基、具体的には炭素数2以上、好ましくは3以上で直鎖状、分岐状、環状構造を有する置換基、より好ましくは分岐状または環状構造を有する置換基が結合しているものが望ましい。また2個以上のエーテル結合間に存在する原子に複数の、好ましくは3〜20、さらに好ましくは3〜10、特に好ましくは3〜7の炭素原子が含まれた化合物が好ましい。 In the polyether compound (c-2) used for the supported titanium-based catalyst, the atoms present between the ether bonds are at least one selected from the group consisting of carbon, silicon, oxygen, sulfur, phosphorus and boron, The number of atoms is 2 or more. Among these, a substituent which is relatively bulky at an atom between ether bonds, specifically, a substituent having 2 or more carbon atoms, preferably 3 or more and having a linear, branched or cyclic structure, more preferably branched or Those having a substituent having a cyclic structure are desirable. A compound in which a plurality of, preferably 3 to 20, more preferably 3 to 10, and particularly preferably 3 to 7 carbon atoms are contained in atoms present between two or more ether bonds is preferable.
このようなポリエーテル化合物(c−2)のうち好ましい化合物は1,3−ジエーテル類で、特に2,2−ジイソブチル−1,3−ジメトキシプロパン、2−イソプロピル−2−イソペンチル−1,3−ジメトキシプロパン、2,2−ジシクロヘキシル−1,3−ジメトキシプロパン、2,2−ビス(シクロヘキシルメチル)−1,3−ジメトキシプロパンが好ましく用いられる。 Among such polyether compounds (c-2), preferred compounds are 1,3-diethers, particularly 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3- Dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, and 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane are preferably used.
上記の固体状チタン触媒成分(a)または(a’)は、公知の方法を含むあらゆる方法を採用して調製することができる。例えば固体状チタン触媒成分(a)は、一般的にはマグネシウム化合物、チタン化合物および電子供与体を接触させることにより調製することができる。 The solid titanium catalyst component (a) or (a ′) can be prepared by any method including known methods. For example, the solid titanium catalyst component (a) can be generally prepared by contacting a magnesium compound, a titanium compound and an electron donor.
固体状チタン触媒成分(a)又は(a’)は、重合容積1リットル当りチタン原子換算で、通常0.01〜200ミリモル、好ましくは0.05〜100ミリモルの濃度で用いられることが望ましい。 The solid titanium catalyst component (a) or (a ′) is desirably used in a concentration of usually 0.01 to 200 mmol, preferably 0.05 to 100 mmol, in terms of titanium atom per liter of polymerization volume.
有機金属化合物(b)は、固体状チタン触媒成分(a)又は(a’)中のチタン原子1モル当り通常0.05〜300モル、好ましくは0.1〜100モルの量で用いることが望ましい。 The organometallic compound (b) is usually used in an amount of 0.05 to 300 mol, preferably 0.1 to 100 mol, per mol of titanium atom in the solid titanium catalyst component (a) or (a ′). desirable.
また電子供与体(c)は、チタン触媒成分(a)または(a’)中のチタン原子1モル当り0.001〜300モル、好ましくは0.01〜200モルの量である。なお、全重合時には電子供与体(c)を用いないことも可能である。 Further, the electron donor (c) is in an amount of 0.001 to 300 mol, preferably 0.01 to 200 mol, per mol of titanium atom in the titanium catalyst component (a) or (a ′). In addition, it is also possible not to use an electron donor (c) at the time of all the polymerization.
本発明ではポリプロピレン樹脂を製造するに際して、上記のような固体状チタン触媒成分(a)又は(a’)、有機金属化合物(b)および電子供与体(c)からなる触媒を用いて、予め前重合を行うこともできる。なお、前重合においては電子供与体(c)を必ずしも用いなくともよい。 In the present invention, when a polypropylene resin is produced, a catalyst comprising the solid titanium catalyst component (a) or (a ′), the organometallic compound (b) and the electron donor (c) as described above is used in advance. Polymerization can also be performed. In the prepolymerization, the electron donor (c) is not necessarily used.
前重合は、固体状チタン触媒成分(a)又は(a’)1g当り0.1〜1000g程度、好ましくは0.3〜500g程度の重合体が生成するように行うことが望ましい。前重合量が多すぎると、本重合における(共)重合体の生成効率が低下することがあり、得られる(共)重合体からシートまたはフィルムなどを成形した場合にフィッシュアイが発生し易くなる場合がある。 The prepolymerization is desirably performed so that about 0.1 to 1000 g, preferably about 0.3 to 500 g of a polymer is formed per 1 g of the solid titanium catalyst component (a) or (a ′). If the amount of prepolymerization is too large, the production efficiency of the (co) polymer in the main polymerization may be reduced, and fish eyes are likely to occur when a sheet or film is formed from the obtained (co) polymer. There is a case.
また、本発明に関わる重合触媒としては、メタロセン化合物と有機アルミニウムとを含むメタロセン系重合触媒を用いることもできる。メタロセン化合物としては、例えばWO2004/029062公開公報やWO2005/019283公開公報に開示されたメタロセン化合物を挙げることができ、本発明に係るポリプロピレンの重合ではこれらを含むメタロセン系重合触媒を制
限無く使用することができる。
In addition, as the polymerization catalyst according to the present invention, a metallocene polymerization catalyst containing a metallocene compound and organoaluminum can also be used. Examples of the metallocene compound include metallocene compounds disclosed in WO2004 / 029062 and WO2005 / 019283. In the polymerization of polypropylene according to the present invention, a metallocene-based polymerization catalyst containing these is used without limitation. Can do.
次に、本発明に係る失活工程について、失活剤として使用される化合物、その調製方法および失活剤の添加量等を説明する。
本発明に係る失活剤は、下記一般式[I]で表される化合物(p)である。
Next, regarding the deactivation step according to the present invention, the compound used as a deactivation agent, its preparation method, the addition amount of the deactivation agent, and the like will be described.
The quencher according to the present invention is a compound (p) represented by the following general formula [I].
R1−O−R−O−R2 ---------- [I]
上記一般式[I]において、R1およびR2は、水素原子、炭素数1〜20のアルキル基
、炭素数6〜30のアリール基、炭素数1〜20のアシル基から選ばれ、相互に同一でも異なっていてもよい。Rはエーテル結合またはエステル結合を含んでいてもよい、炭素数2以上の炭化水素基である。
R 1 -O-R-O-R 2 ---------- [I]
In the general formula [I], R 1 and R 2 are selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an acyl group having 1 to 20 carbon atoms. It may be the same or different. R is a hydrocarbon group having 2 or more carbon atoms, which may contain an ether bond or an ester bond.
一般式[I]におけるR1およびR2としての炭素数1〜20のアルキル基として、具体
的にはメチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、オクチル基、ノニル基などの直鎖状または分岐状のアルキル基を例示できる。炭素数6〜30のアリール基としては、フェニル、ベンジル、ナフチル、ビフェニル、ターフェニル、フェナントリル、アントラセニルなどの基を例示できる。炭素数1〜20のアシル基としては、下記一般式:
−(CO)R'〔R';メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、オクチル基、ノニル基等〕で表される基が例示される。
As the alkyl group having 1 to 20 carbon atoms as R 1 and R 2 in the general formula [I], specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, nonyl group Examples thereof include linear or branched alkyl groups such as Examples of the aryl group having 6 to 30 carbon atoms include phenyl, benzyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl and the like. Examples of the acyl group having 1 to 20 carbon atoms include the following general formula:
Examples include groups represented by-(CO) R '[R': methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, nonyl group, etc.].
一般式[I]におけるRは、エーテル結合またはエステル結合を含んでいてもよい、炭
素数2以上の炭化水素基であって、好ましくは炭素数14以上の炭化水素基である。エーテル結合またはエステル結合は該炭化水素基の主鎖部にあってもよいし側鎖部にあってもよいが、Rとしてはエーテル結合が主鎖部に位置規則的に導入された炭化水素基が好まし
く用いられる。
R in the general formula [I] is a hydrocarbon group having 2 or more carbon atoms, and preferably a hydrocarbon group having 14 or more carbon atoms, which may contain an ether bond or an ester bond. The ether bond or the ester bond may be in the main chain portion or the side chain portion of the hydrocarbon group, and R is a hydrocarbon group in which ether bonds are introduced into the main chain portion in a regioregular manner. Is preferably used.
また、上記一般式[I]で表される化合物の分子量は、通常500以上、好ましくは5
00〜10000、より好ましくは600〜4000、更に好ましくは700〜2500である。分子量が500未満では、回収したモノマーおよび溶媒を重合系に再利用する際に触媒活性の低下、著しい場合は触媒活性が発現しない場合があるので好ましくない。過大な分子量は、液化プロピレンやヘプタンなどの溶媒に不溶になるためため好ましくない。
The molecular weight of the compound represented by the above general formula [I] is usually 500 or more, preferably 5
It is 00-10000, More preferably, it is 600-4000, More preferably, it is 700-2500. When the molecular weight is less than 500, the recovered monomer and solvent are not preferable because the catalytic activity is lowered when the recovered monomer and solvent are reused in the polymerization system. An excessive molecular weight is not preferable because it becomes insoluble in a solvent such as liquefied propylene or heptane.
一般式[I]で表される化合物(p)は、末端基が水素原子であるか否かによって下記一般式[I-1]、[I-2]および[I-3]で表される3種類の化合物に分類される。 The compound (p) represented by the general formula [I] is represented by the following general formulas [I-1], [I-2] and [I-3] depending on whether or not the terminal group is a hydrogen atom. There are three types of compounds.
H−O−R−O−H ---------- [I-1] H-O-R-O-H ---------- [I-1]
R1−O−R−O−H ---------- [I-2] R 1 −O−R−O−H ---------- [I-2]
R1−O−R−O−R2 ---------- [I-3]
上記一般式[I-1]〜[I-3]において、R、R1およびR2は一般式[I]において定義され
た各々R、R1およびR2と同義である。
R 1 −O−R−O−R 2 ---------- [I-3]
In the general formulas [I-1] to [I-3], R, R 1 and R 2 have the same meanings as R, R 1 and R 2 defined in the general formula [I], respectively.
これら3種類の化合物は、分子量が500以上であるという条件を満たす限り、失活剤として制限無く使用が可能であるが、回収モノマーや回収溶剤への失活剤混入量の視点からは、両末端が水素原子である一般式[I-1]で表されるジオール系化合物が好ましい。 These three types of compounds can be used without limitation as a deactivator as long as the molecular weight is 500 or more, but from the viewpoint of the amount of deactivator mixed in the recovered monomer or recovered solvent, A diol compound represented by the general formula [I-1] whose terminal is a hydrogen atom is preferred.
一般式[I]で表される化合物(p)の好ましい形態としては、下記一般式[II]で表さ
れるグリコール系の化合物(q)が挙げられる。
Preferable forms of the compound (p) represented by the general formula [I] include a glycol compound (q) represented by the following general formula [II].
R1−O−[CH2−CH(R3)−O]k−R2 ---------- [II]
上記一般式[II]において、R1、R2は前記一般式[I]におけるR1、R2に各々同義であ
り、炭素数1〜20のアルキル基、炭素数6〜30のアリール基および炭素数1〜20のアシル基についても、R1、R2で例示した基を制限無く使用することができる。R3は、
水素原子、炭素数1〜20のアルキル基、炭素数6〜30のアリール基および炭素数1〜20のアシル基から選ばれ、相互に同一でも異なっていてもよい。R3の好ましい態様は
、水素原子又はメチル基である。kは平均繰り返し単位数を表わし、通常1〜100の範
囲、好ましくは5〜50の範囲である。
R 1 -O- [CH 2 -CH (R 3 ) -O] k -R 2 ---------- [II]
In the above general formula [II], R 1, R 2 are each synonymous R 1, R 2 in the general formula [I], the alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms and For the acyl group having 1 to 20 carbon atoms, the groups exemplified for R 1 and R 2 can be used without limitation. R 3 is
It is selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an acyl group having 1 to 20 carbon atoms, which may be the same as or different from each other. A preferred embodiment of R 3 is a hydrogen atom or a methyl group. k represents the average number of repeating units, and is usually in the range of 1 to 100, preferably in the range of 5 to 50.
このような化合物(q)として具体的には、ポリオキシエチレンラウリルエーテル、ポ
リオキシエチレンオレイルエーテル、ポリオキシアルキレンラウリルエーテル、ポリオキシエチレンイソデシルエーテル、ポリオキシエチレンアルキルエーテル、ポリオキシアルキレンアルキルエーテル、ポリオキシエチレンヒマシ油、ポリオキシエチレン硬化ヒマシ油、ポリオキシエチレンスチレン化フェニルエーテル、ポリオキシエチレンオレイン酸エステル、ポリオキシエチレンジステアリン酸エステル、ポリオキシアルキレングリコール、ソルビタンセスキオレエート、ソルビタンモノオレエート、ソルビタンモノステアレート、ソルビタンモノラウレート、ポリオキシエチレンソルビタンモノラウレート、ポリオキシエチレンソルビタンモノステアレート、ポリオキシエチレンソルビタンモノオレエート、ポリオキシエチレンラノリンアルコールエーテル、ポリオキシエチレンラノリン脂肪酸エステル、ポリオキシエチレンアルキルアミンエーテル、ポリエチレングリコールアルキルエーテル、ポリエチレングリコールモノラウレート、ポリエチレングリコールモノステアレート、ポリエチレングリコールモノオレエート、ポリエチレングリコールソルビタンモノラウレート、ポリエチレングリコールソルビタンモノオレエートなどが挙げられる。
Specific examples of such compound (q) include polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyalkylene lauryl ether, polyoxyethylene isodecyl ether, polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, Polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene styrenated phenyl ether, polyoxyethylene oleate, polyoxyethylene distearate, polyoxyalkylene glycol, sorbitan sesquioleate, sorbitan monooleate, Sorbitan monostearate, sorbitan monolaurate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate Allate, polyoxyethylene sorbitan monooleate, polyoxyethylene lanolin alcohol ether, polyoxyethylene lanolin fatty acid ester, polyoxyethylene alkylamine ether, polyethylene glycol alkyl ether, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol Examples include monooleate, polyethylene glycol sorbitan monolaurate, and polyethylene glycol sorbitan monooleate.
一般式[I]で表される化合物(p)のより好ましい形態は、下記一般式[III]で表さ
れるポリオキシエチレンオキシプロピレン重合体(r)である。
A more preferable form of the compound (p) represented by the general formula [I] is a polyoxyethyleneoxypropylene polymer (r) represented by the following general formula [III].
HO−(C2H4O)a−(C3H6O)b−(C2H4O)c−H ---------- [III]
上記一般式[III]において、a,bおよびcは平均繰返し単位数を表し、各々1〜1
00の範囲である。(C2H4O)で表されるオキシエチレン単位の繰返し単位数を示すa及び
cの合計(a+c)は、好ましくは2〜40、より好ましくは4〜20、さらに好ましくは4〜15の範囲である。一方、(C3H6O)で表されるオキシプロピレン単位の繰返し単位
数を示すbは、好ましくは2〜50、より好ましくは10〜50、さらに好ましくは20〜50の範囲である。a,bおよびcのいずれかが100を超える分子量が過大な重合体(r)は、液化プロピレンやヘプタンなどの溶媒に不溶なため好ましくない。また、オキ
シエチレン単位の割合が過大であることも、液化プロピレンやヘプタンなどの溶媒に不溶となる場合があるので好ましくない。
HO− (C 2 H 4 O) a − (C 3 H 6 O) b − (C 2 H 4 O) c −H ---------- [III]
In the above general formula [III], a, b and c represent the average number of repeating units, each of 1 to 1
The range is 00. The total (a + c) of a and c indicating the number of repeating units of the oxyethylene unit represented by (C 2 H 4 O) is preferably 2 to 40, more preferably 4 to 20, and further preferably 4 to 15. It is a range. On the other hand, b indicating the number of repeating units of the oxypropylene unit represented by (C 3 H 6 O) is preferably in the range of 2 to 50, more preferably 10 to 50, and still more preferably 20 to 50. A polymer (r) having an excessive molecular weight of any one of a, b and c exceeding 100 is not preferable because it is insoluble in a solvent such as liquefied propylene or heptane. In addition, an excessive proportion of oxyethylene units is not preferable because it may become insoluble in a solvent such as liquefied propylene or heptane.
本発明に係る失活剤、すなわち上記の化合物(p)、(q)または(r)の添加量は、有
機アルミ量に対して、通常50〜1000モル%、好ましくは70〜500モル%、更に好ましくは100〜400モル%の範囲の量である。
The added amount of the quenching agent according to the present invention, that is, the compound (p), (q) or (r) is usually 50 to 1000 mol%, preferably 70 to 500 mol%, based on the amount of organic aluminum. More preferably, the amount is in the range of 100 to 400 mol%.
失活剤は重合工程後、生成された重合体、未反応の単量体、触媒、さらに溶媒重合法においては溶媒が混合したスラリーに、上記の所定の量、添加すればよい。失活剤は、そのまま使用することも、適当な溶媒に希釈して使用することもできる。 After the polymerization step, the deactivator may be added to the produced polymer, unreacted monomer, catalyst, and, in the solvent polymerization method, the above-mentioned predetermined amount to the slurry mixed with the solvent. The quenching agent can be used as it is or diluted in an appropriate solvent.
モノマーおよび溶媒の回収の方法は、例えば上記のように失活剤を添加したスラリーを
ガス化して気固分離し、ガス成分を分留等によりモノマー成分と溶媒成分とに分離すればよい。
As a method for recovering the monomer and the solvent, for example, the slurry added with the deactivator as described above may be gasified and gas-solid separated, and the gas component may be separated into the monomer component and the solvent component by fractional distillation or the like.
このとき、本発明による失活剤は、ガス成分すなわちモノマー成分と溶媒成分とに混入することがない。したがって、失活剤の影響で触媒活性が低下するという問題が発生することなく、回収したモノマーおよび溶媒を再び重合に使用できる。 At this time, the quenching agent according to the present invention is not mixed into the gas component, that is, the monomer component and the solvent component. Therefore, the recovered monomer and solvent can be used again for the polymerization without causing a problem that the catalytic activity is lowered due to the influence of the deactivator.
以下、本発明を実施例に基づきさらに詳細に説明するが、本発明はかかる実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to this Example.
[固体状チタン触媒成分(a)の調製]
無水塩化マグネシウム952g、デカン4420mlおよび2−エチルヘキシルアルコール3906gを、130℃で2時間加熱して均一溶液とした。この溶液中に無水フタル酸213gを添加し、130℃にてさらに1時間攪拌混合を行って無水フタル酸を溶解させた。
[Preparation of solid titanium catalyst component (a)]
952 g of anhydrous magnesium chloride, 4420 ml of decane and 3906 g of 2-ethylhexyl alcohol were heated at 130 ° C. for 2 hours to obtain a homogeneous solution. To this solution, 213 g of phthalic anhydride was added, and further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride.
このようにして得られた均一溶液を23℃まで冷却した後、この均一溶液の750mlを、−20℃に保持された四塩化チタン2000ml中に1時間にわたって滴下した。滴下後、得られた混合液の温度を4時間かけて110℃に昇温し、110℃に達したところでフタル酸ジイソブチル(DIBP)52.2gを添加し、これより2時間攪拌しながら同温度に保持した。次いで熱時濾過にて固体部を採取し、この固体部を2750mlの四塩化チタンに再懸濁させた後、再び110℃で2時間加熱した。 After cooling the homogeneous solution thus obtained to 23 ° C., 750 ml of this homogeneous solution was dropped into 2000 ml of titanium tetrachloride maintained at −20 ° C. over 1 hour. After the dropwise addition, the temperature of the resulting mixture was raised to 110 ° C. over 4 hours. When the temperature reached 110 ° C., 52.2 g of diisobutyl phthalate (DIBP) was added, and the mixture was stirred at the same temperature for 2 hours. Held on. Subsequently, the solid part was collected by hot filtration, and the solid part was resuspended in 2750 ml of titanium tetrachloride, and then heated again at 110 ° C. for 2 hours.
加熱終了後、再び熱濾過にて固体部を採取し、110℃のデカンおよびヘキサンを用いて、洗浄液中にチタン化合物が検出されなくなるまで洗浄した。
上記の様に調製された固体状チタン触媒成分(a)はヘキサンスラリーとして保存されるが、このうち一部を乾燥して触媒組成を調べた。固体状チタン触媒成分(a)は、チタンを2重量%、塩素を58重量%、マグネシウムを19重量%およびDIBPを21重量%の量で含有していた。
[前重合触媒の調製]
遷移金属触媒成分80g、トリエチルアルミニウム14mL、ヘプタン80Lを内容量200Lの攪拌機付きオートクレーブに挿入し、内温5℃に保ちプロピレンを800g挿入し、60分間攪拌しながら反応させた。重合終了後、固体成分を沈降させ、上澄み液の除去およびヘプタンによる洗浄を2回行った。得られた前重合触媒を精製ヘプタンに再懸濁して、遷移金属触媒成分濃度で1g/Lとなるよう、ヘプタンにより調整を行った。この前重合触媒は遷移金属触媒成分1g当りポリプロピレンを10g含んでいた。
[重合]
内容積500Lの重合槽にプロピレンを130kg/時間、触媒として上記前処理を施した遷移金属触媒成分を1.7g/時間とトリエチルアルミニウム4.3g/時間とジシクロペンチルジメトキシシラン2.9g/時間を連続的に供給した。第1重合槽の温度は70℃、水素を気相部の水素濃度が4.0モル%になるように供給した。平均反応量は30000g−PP/g遷移金属触媒成分であった。重合槽を出たスラリーは、触媒失活槽に送られ、触媒失活した。温度65℃、失活剤として、ポリオキシエチレン−ポリオキシプロピレン重合体をトリエチルアルミニウムに対し、360モル%装入した。触媒失活槽から、フラッシュ管を通し、スラリーをガス化した後、気固分離し、重合パウダーを回収した。パウダーは50kg/時間で得られ、80℃、70mmHgで10時間乾燥して製品パウダーとした。ガス成分は、コンデンスした後で、プロピレン主成分とヘプタン主成分に分離した。プロピレン成分は、蒸留回収し、昇圧後、重合槽に供給した。また、ヘプタン成分は蒸留回収し、この蒸留したヘプタンを用い、前重合触媒を調製し、同様に重合
を行った。
[比較例1]
重合を次の様に変更した以外は、実施例1と同様に行った。
[重合]
内容積500Lの重合槽にプロピレンを130kg/時間、触媒として上記前処理を施した遷移金属触媒成分を1.7g/時間とトリエチルアルミニウム4.3g/時間とジシクロペンチルジメトキシシラン2.9g/時間を連続的に供給した。第1重合槽の温度は70℃、水素を気相部の水素濃度が4.0モル%になるように供給した。平均反応量は30000g−PP/g遷移金属触媒成分であった。重合槽を出たスラリーは、触媒失活槽に送られ、触媒失活した。温度65℃、失活剤として、ジエチレングリコールモノイソプロピルエーテルをトリエチルアルミニウムに対し、360モル%装入した。触媒失活槽から、フラッシュ管を通し、スラリーをガス化した後、気固分離し、重合パウダーを回収した。パウダーは50kg/時間で得られ、80℃、70mmHgで10時間乾燥して製品とした。ガス成分は、コンデンスした後で、プロピレン主成分とヘプタン主成分に分離した。プロピレン成分は、蒸留回収し、昇圧後、重合槽に供給した。また、ヘプタン成分は蒸留回収し、この蒸留したヘプタンを用い、前重合触媒を調製し、同様に重合を行った。[比較例2]
重合を次の様に変更した以外は、実施例1と同様に行った。
[重合]
内容積500Lの重合槽にプロピレンを130kg/時間、触媒として上記前処理を施した遷移金属触媒成分を1.7g/時間とトリエチルアルミニウム4.3g/時間とジシクロペンチルジメトキシシラン2.9g/時間を連続的に供給した。第1重合槽の温度は70℃、水素を気相部の水素濃度が4.0モル%になるように供給した。平均反応量は30000g−PP/g遷移金属触媒成分であった。重合槽を出たスラリーは、触媒失活槽に送られ、触媒失活した。温度65℃、失活剤として、酢酸ブチルをトリエチルアルミニウムに対し、360モル%装入した。触媒失活槽から、フラッシュ管を通し、スラリーをガス化した後、気固分離し、重合パウダーを回収した。パウダーは50kg/時間で得られ、80℃、70mmHgで10時間乾燥して製品とした。ガス成分は、コンデンスした後で、プロピレン主成分とヘプタン主成分に分離した。プロピレン成分は、蒸留回収し、昇圧後、重合槽に供給した。また、ヘプタン成分は蒸留回収し、この蒸留したヘプタンを用い、前重合触媒を調製し、同様に重合を行った。
After the heating, the solid part was again collected by hot filtration, and washed with decane and hexane at 110 ° C. until no titanium compound was detected in the washing solution.
The solid titanium catalyst component (a) prepared as described above was stored as a hexane slurry. A part of the catalyst was dried to examine the catalyst composition. The solid titanium catalyst component (a) contained 2% by weight of titanium, 58% by weight of chlorine, 19% by weight of magnesium and 21% by weight of DIBP.
[Preparation of prepolymerization catalyst]
80 g of transition metal catalyst component, 14 mL of triethylaluminum, and 80 L of heptane were inserted into an autoclave equipped with a stirrer having an internal volume of 200 L, and 800 g of propylene was inserted while maintaining the internal temperature at 5 ° C., and reacted for 60 minutes. After completion of the polymerization, the solid component was precipitated, and the supernatant was removed and washed with heptane twice. The obtained prepolymerization catalyst was resuspended in purified heptane and adjusted with heptane so that the transition metal catalyst component concentration was 1 g / L. This prepolymerization catalyst contained 10 g of polypropylene per 1 g of the transition metal catalyst component.
[polymerization]
In a polymerization tank having an internal volume of 500 L, propylene was added at 130 kg / hour, the transition metal catalyst component pretreated as the catalyst was 1.7 g / hour, triethylaluminum 4.3 g / hour, and dicyclopentyldimethoxysilane 2.9 g / hour. Continuously fed. The temperature of the first polymerization tank was 70 ° C., and hydrogen was supplied so that the hydrogen concentration in the gas phase portion was 4.0 mol%. The average reaction amount was 30000 g-PP / g transition metal catalyst component. The slurry exiting the polymerization tank was sent to the catalyst deactivation tank and deactivated. At a temperature of 65 ° C., 360 mol% of a polyoxyethylene-polyoxypropylene polymer was charged as a deactivator with respect to triethylaluminum. From the catalyst deactivation tank, the slurry was gasified through a flash tube, and then gas-solid separation was performed to recover the polymerization powder. The powder was obtained at 50 kg / hour and dried at 80 ° C. and 70 mmHg for 10 hours to obtain a product powder. After condensing, the gas component was separated into a propylene main component and a heptane main component. The propylene component was recovered by distillation, and after pressurization, was supplied to the polymerization tank. Further, the heptane component was recovered by distillation, a prepolymerized catalyst was prepared using this distilled heptane, and polymerization was performed in the same manner.
[Comparative Example 1]
The same procedure as in Example 1 was performed except that the polymerization was changed as follows.
[polymerization]
In a polymerization tank having an internal volume of 500 L, propylene was added at 130 kg / hour, the transition metal catalyst component pretreated as the catalyst was 1.7 g / hour, triethylaluminum 4.3 g / hour, and dicyclopentyldimethoxysilane 2.9 g / hour. Continuously fed. The temperature of the first polymerization tank was 70 ° C., and hydrogen was supplied so that the hydrogen concentration in the gas phase portion was 4.0 mol%. The average reaction amount was 30000 g-PP / g transition metal catalyst component. The slurry exiting the polymerization tank was sent to the catalyst deactivation tank and deactivated. At a temperature of 65 ° C., 360 mol% of diethylene glycol monoisopropyl ether as a deactivator was added to triethylaluminum. From the catalyst deactivation tank, the slurry was gasified through a flash tube, and then gas-solid separation was performed to recover the polymerization powder. The powder was obtained at 50 kg / hour, and dried at 80 ° C. and 70 mmHg for 10 hours to obtain a product. After condensing, the gas component was separated into a propylene main component and a heptane main component. The propylene component was recovered by distillation, and after pressurization, was supplied to the polymerization tank. Further, the heptane component was recovered by distillation, a prepolymerized catalyst was prepared using this distilled heptane, and polymerization was performed in the same manner. [Comparative Example 2]
The same procedure as in Example 1 was performed except that the polymerization was changed as follows.
[polymerization]
In a polymerization tank having an internal volume of 500 L, propylene was added at 130 kg / hour, the transition metal catalyst component pretreated as the catalyst was 1.7 g / hour, triethylaluminum 4.3 g / hour, and dicyclopentyldimethoxysilane 2.9 g / hour. Continuously fed. The temperature of the first polymerization tank was 70 ° C., and hydrogen was supplied so that the hydrogen concentration in the gas phase portion was 4.0 mol%. The average reaction amount was 30000 g-PP / g transition metal catalyst component. The slurry exiting the polymerization tank was sent to the catalyst deactivation tank and deactivated. At a temperature of 65 ° C., 360 mol% of butyl acetate as a deactivator was charged with respect to triethylaluminum. From the catalyst deactivation tank, the slurry was gasified through a flash tube, and then gas-solid separation was performed to recover the polymer powder. The powder was obtained at 50 kg / hour, and dried at 80 ° C. and 70 mmHg for 10 hours to obtain a product. After condensing, the gas component was separated into a propylene main component and a heptane main component. The propylene component was recovered by distillation, and after pressurization, was supplied to the polymerization tank. Further, the heptane component was recovered by distillation, a prepolymerized catalyst was prepared using this distilled heptane, and polymerization was performed in the same manner.
本発明のポリプロピレン製造法は、容易にモノマー、溶媒を回収、再利用できるポリプ
ロピレン製造方法である。
The polypropylene production method of the present invention is a polypropylene production method in which monomers and solvents can be easily recovered and reused.
Claims (3)
ルミニウム化合物量に対して50〜1000モル%の範囲の量で添加することを特徴とするポリプロピレンの製造方法;
R1−O−R−O−R2 ---------- [I]
(上記一般式[I]において、R1およびR2は、水素原子、炭素数1〜20のアルキル
基、炭素数6〜30のアリール基、炭素数1〜20のアシル基から選ばれ、相互に同一でも異なっていてもよい。Rはエーテル結合またはエステル結合を含んでいてもよい、炭素数2以上の炭化水素基を示す。) In the presence of a polymerization catalyst containing an organoaluminum compound, a polymerization step in which propylene is homopolymerized or copolymerized with propylene and another olefin by a solvent method or a bulk method, and a deactivation step in which the polymerization catalyst is deactivated. In the deactivation step, the compound represented by the following general formula [I] having a molecular weight of 500 or more as a deactivator in the deactivation step is in the range of 50 to 1000 mol% with respect to the amount of the organoaluminum compound. A process for producing polypropylene, characterized in that it is added in an amount of
R 1 -O-R-O-R 2 ---------- [I]
(In the above general formula [I], R 1 and R 2 are selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an acyl group having 1 to 20 carbon atoms; And R represents a hydrocarbon group having 2 or more carbon atoms, which may contain an ether bond or an ester bond.)
R1−O−[CH2−CH(R3)−O]k−R2 ---------- [II]
(上記一般式[II]において、R1、R2およびR3は、水素原子、炭素数1〜20のア
ルキル基、炭素数6〜30のアリール基および炭素数1〜20のアシル基から選ばれ、相互に同一でも異なっていてもよい。kは平均繰り返し単位数を表わし、1〜100の範囲
である。) The method for producing polypropylene according to claim 1, wherein the deactivator is a compound represented by the following general formula [II];
R 1 -O- [CH 2 -CH (R 3 ) -O] k -R 2 ---------- [II]
(In the general formula [II], R 1 , R 2 and R 3 are selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms and an acyl group having 1 to 20 carbon atoms. And may be the same or different from each other, k represents the average number of repeating units and is in the range of 1 to 100.)
は2記載のポリプロピレンの製造方法。
HO-(C2H4O)a-(C3H6O)b-(C2H4O)c-H ---------- [III]
(上記一般式[III]において、a,b,cは平均繰り返し単位数を表わし、各々1〜100の範囲である。) The method for producing polypropylene according to claim 1 or 2, wherein the quenching agent is a compound represented by the following general formula [III].
HO- (C 2 H 4 O) a- (C 3 H 6 O) b- (C 2 H 4 O) c -H ---------- [III]
(In the above general formula [III], a, b, and c represent the average number of repeating units, each ranging from 1 to 100.)
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JPS5922910A (en) * | 1982-07-29 | 1984-02-06 | Sumitomo Chem Co Ltd | Manufacture of ethylene polymer or ethylene copolymer |
JPS59176306A (en) * | 1983-03-28 | 1984-10-05 | Asahi Chem Ind Co Ltd | Production of polyethylene |
JPS61266412A (en) * | 1985-05-21 | 1986-11-26 | Mitsui Toatsu Chem Inc | Recovery of polymerization solvent |
JPH05214007A (en) * | 1990-03-26 | 1993-08-24 | Shell Oil Co | Process for producing impact-resistant copolymer |
JP2007023154A (en) * | 2005-07-15 | 2007-02-01 | Mitsui Chemicals Inc | Olefin based polymer particle and method for producing olefin based polymer particle |
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JPS5922910A (en) * | 1982-07-29 | 1984-02-06 | Sumitomo Chem Co Ltd | Manufacture of ethylene polymer or ethylene copolymer |
JPS59176306A (en) * | 1983-03-28 | 1984-10-05 | Asahi Chem Ind Co Ltd | Production of polyethylene |
JPS61266412A (en) * | 1985-05-21 | 1986-11-26 | Mitsui Toatsu Chem Inc | Recovery of polymerization solvent |
JPH05214007A (en) * | 1990-03-26 | 1993-08-24 | Shell Oil Co | Process for producing impact-resistant copolymer |
JP2007023154A (en) * | 2005-07-15 | 2007-02-01 | Mitsui Chemicals Inc | Olefin based polymer particle and method for producing olefin based polymer particle |
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